Process for the production of gasolene and naphtha from crude oils, petroleum products, tar-oil, or similar products.



P. DANCKWARDT. PROCESS FOR THE PRODUCTION OF GASOLENE AND NAPHTHA FROM CRUDE OILS, PETROLEUM PRODUCTS, TAR OIL, 0R SIMILAR PRODUCTS. APPLICATION FILED MAR. 4. 1914.

Patented June 1, 1915.

ZlZ M STATES PATENT OFFICE.

DAYCKWARDT, OF NEAR DARDANELLE, ARKANSAS.

mm N! THE PRODUCTION 0] GASOLENE AND NAPH'IHA FROM CRUDE 0-1145, PETROLEUM PRODUCTS, TAR-OIL, OB, SIMILAR PRODUCTS.

Specification of Letters Qatent.

Patented June 1, 1915.

Application filed March 4, 1914. Serial No. 822,282.

ducing gasolene from coal oil (petroleum),

its constituents and similar oils. It is a known fact that by simple distillation of these materials a certain amount of gasoleno is obtained, and also that by the process of destructive distillation a somewhat larger amount can be obtained, particularly when performed under pressure. The latter process, however, has the objectionable feature that it destroys the stills quickly and is extremely dangerous when carried out under pressure.

The ob'ect of my invention is to obviate these di culties and to produce a much larger amount of gasolene from the same amount of oil than other processes will yield. At the same time this process can utilize the expansive force of the generated vapors and gases for the production of power as a byproduct, when oonducted in or in connection with an apparatus formerly patented by me. In my Patent 1023819 I proposed to produce power by introducing coal oil and similar products into a heated fluid medium (molten lead, alloy, etc.,) thereby causing the oil to be volatilized, and to use the expansive force of the gases for the production of ower. When this process is conducted at the higher temperatures, the recondensed oil shows an increased amount of lighter hydrocarbons, and this amount increases.

right along, when the oil is used over again, so that gradually all the oil can be changed into lighter hydrocarbons, commonly called naphtha, of which gasolene forms a certain fraction.

The conditions for the successful, economical destructive, distillation for the purpose of producing the largest possible amount of naphtha and gasolene from oils are high pressure, and consequently an elevated temperature as otherwise the oil would cease boiling at the higher pressure and aneven heat, so that no local overheating can take place, which would cause the formation of is for instance possible by forcing much gas and carbon, while for the purpose n View, the breaking up of the crude ,oil shall not proceed that far. To make this latter statement clearer, I will state that it Oll through red hot tubes to almost comp etely break up the constituents of the oil into 'fixed gas and carbon without the formation of any naphtha, if the vapors remain long enough in contact with the highly overheated pipes. It must be then an elevated temperature which should be well controlled. It is however impossible to obtain such a result with an apparatus which is fitwardly heated by direct fire, however carefull the pressure inside of the still may be regu 'ated or whatever means may be used (gas, steam, etc.,) to carry off as fast as possible, the vapors from the walls. Retorts, whether common or tubular, if fired directly from the outside,- have therefore proved failures in all cases, not only on account of the uneven heat supply, but also on account of the darn ger caused by deposit of coke and by the local overheating. It has been the aim of chemists to avoid these troubles by the .introduction of a heat carrier,'gases and steam having been mainly recommended, while others have recommended to heat the retort outwardly. by such heating medium. Although this is a good device in the laboratory and often used, in order to apply this scheme on a commercial scale, the apparatus obtains too large dimensions, because the heat cannot be transmitted fast enough to the oil, unless very large surface is given. The surface must indeed be very much larger than in the cases where the still is heated by direct fire, as the difference of temperatures within and without the walls is much smaller than in the above case. We must look then for heat carriers, which can be brought inside of. the still into direct contact with the oil, bywhich the problem can be solved, and here it is true that those I process I will give the results on an oil with a rather heavy base, which gave by common fractional distillation at atmospheric pres-- sure 7% light hydrocarbons of a boiling point up to 150 0., 32% of a boiling point up to 250 C. and the rest of a boilin point above 250 C. When this oil was so jected to my process under a pressure of about 125 lbs. per square inch and at a temperature of about 400 centigrade, it gave in one distillation; 65% naphtha boiling point up to 150 C., 20% of a boiling point up to 250 0., 10% of a boiling point above 250 C. containing some carbon, and 5% fixed gas. By returning the fractions boiling at 250 C. and that boiling above 253 C. there was obtained 15% more naphtha. boiling point up to 150 C. and 7% of a boiling point up to 250 C., the rest of a boiling point above 250 C. A- third operation increased the total of naphtha by only 5%. In actual practice these undecomposed fractlons will,

generally, not be worked up for themselves.

I presumed this to be done only for the purpose of showing the progress of the process when the distillation is repeated with those portions that did not break up at once. In practice they will best be added to fresh oil in order to always keep the composition of the oil entering the still as much alike-as possible unless they are cut out 01' the proc ess alto ether and worked up for the production of special oils where there may be a better demand for such.

The present process may, therefore, be performed in the same apparatus as illustrated in the above patent or in that shown in my Patents#933022 and #933023. The

chamber consists of at having two valves 11,

power produced will then form a byroduct of value enough to pay for the who e operation. I, however, here show another form of apparatus, which may be used either for itself in cases when power as a by-product is not desired, or in connection with any of the above apparatus in a somewhat simpler form, when power is desired This new apparatus has the advantage of the fire being separated from that part of the apparatus, where the oil is introduced, being conse- .quently less dangerous to o erate, keeping any carbon liberated, out 0 the power apparatus, and evaporating more oil for its size.

In the accompanying drawingi Figure 1 is a vertical section of the separate still with accessories, and Fig. 2 a cross section on line. 2--2,Fig.1'. I

Let the numeral '1 designate the stove in 6 which a metallic coil 2 isheated by a gas or oil burner 3. The upper end of the coil is connected through pipe 4 with the bottom of the still 5. This still consists of an iron Vessel with an iron grating 7 inside, and 1 is inclosed in brickwork 6, or some other good insulator. The still can be heatedby a gas or oil burner 8 The bottom end of the heating coil 2'is connected-through pipe 9 :with a pump chamber 10. gThis pump piece of iron pipe 12, at the inletand barrel 14 I fill with an therefore let the piston 15, operated by some suitable mechanical contrivance (not shown) press directly upon a liquid medium, such as water, oil, etc., suppliedthrough a pipe 19, said medium being contained partly in a barrel 10, and partly in a barrel 14.. Barrel 16 is water-jacketed as at 16 and the jacket haspipes 17, 17", for inlet and outlet of cooling water. The upper space in inert gas (such as carbon dioxid or other suitable gas) under pressure through pipe 18. The pump works therefore in such a way that the piston 15 operates on a liquid, the liquid on a gas, and the gas on the heating medium to be pumped through chamber 10. Through the discharge pipe 20 the heating medium is conveyed to the still 5 in the form of a spray, falling over the grating 7. Another pipe 21 delivers by a pump 22, connected with tanks 23 and 24 through pipes 25 and 20, the oil to be distilled into the still, also in the shape of a spray. The vapor generated in the still passes off through pipe 27, which has a throttling valve 28, to the first condenser 29. This condenser is cooled by any suitable medium which is supplied and discharged through pipes 30 and 31 respectively. The part of the oil condensing in condenser 29 discharges by a pump 32, through pipe 33 into a tank 24. The uncondensed vapors and gases pass through pipe 34 into the second condenser 35, which is operated at a lower temperature to condense the lighter hydrocarbons, and allows any uncondensable (fixed) gases to escape In order to carry out my process in this apparatus, I first light the burners 3 and 8 of the heating coil and the still. When the apparatus issuflficiently hot, I introduce through pipes 40 and 41 the heating medium which mustbe a fluid at the temperature to be applied, and which, if at normal temperature a; solid, must be melted first and then introduced. Several substancesmay be selectedffor this purpose, the main condition of successful use being that the .do not react chemically with the oil to distilled,

or, at least not to any serious extent. I prefer a metal, as for instance lead or an alloy, or an easily fusible salt, as for instance sodium nitrite, or sodium hydrate. When the coil is nearly filled with. the medium and the still is filled up to about the opening of pipe 42, I turn the cooling medium into the little jackets of pipes 40 and 41, whereby the metal contained in these pipes is chilled, solidifies and forms a. perfect plug preventing the escape of any heating medium. The cooling medium must remain turned on as long as the apparatus remains in operation. I now heat the pipes 9, 20, 10 and 4, if any metal or fluid should have solidified in them, with a torch, until no obstruction exists. After this, I introduce so much fluid (oil or water or any suitable fluid) into barrels 16 and 14, that when the piston 15 is at its highest point, the fluid in barrel 14 stands at the line marked in the drawing. I also introduce a gas (carbonic acid or a fixed hydrocarbon) through pipe 18 into barrel 14, while the valve in pipe 13 is shut, until the pressure is somewhat higher than that to be employed in the still. I then open the valve in pipe 13 and start the movement operating the piston 15. This will cause the fluid in barrel 14 to rise and compress the gas in chamber 10, whereby part of the heating fluid is driven out through pipe 20, the valve 12 opening at this phase, while valve 11 closes. At the return or upward stroke of the piston, the gas will be expanded in chamber 10 and allow a fresh part of heating fluid to enter the chamber through open valve 11, which fluid will be driven out through pipe 20 by the next downward stroke, and so on. The metal, or fluid, discharged from the upper end of pipe 20 drops over the iron grating 7 heating the same as well as the whole interior of the still. I continue this, until coil and still have reached the proper temperature, at which destructive distillation is most active for the respective oil under theproper degree of gas pressure. I then turn oil the gas of burner 8, so that the still is now heated only by the metal or fluid circulating between the heating coil and the still. When this phase has been reached, I force some carbonic acid gas through pipe 42 into the still to drive out of it and the condensers all air in order to prevent an explosion. Then I start the pumps 22 and 32 and open valve of pipe 25 slowly. This lets a shower of oil into the still, which upon mingling with the drops of lead or heating fluid above the hot grating, is brought into a prolonged and intimate contact, so that it is evaporated immediately. The process is now to be regulated so that in proportion to the amount of lead or heating fluid circulating such an amount of oil is introduced, that not more than a small layer of highest boiling point (the heaviest part of crude oil) will accumulate on the surface of the heavier heating fluid at the bottom of the still. This can be tested by opening the valve of pipe 42. Valve 28 must be so set that the pressure maintained in the still is the most suitable one for the oil and the temperature. The latter can easily be ascertained by measuring the temperature of the pipes conveying the heating fluid between still and coil. A manometer and safety valve may be placed at convenient places of the still. (Not shown.)

The first condenser is kept at a temperature suitable for condensing all the vapors of hydrocarbons boiling above that of naphtha or gasolene or of those hydrocarbons which it is desired to cut out of the process or to be used over again. They are pumped into tank 24. If to be used over again they may be led through pipe 26 to the pump 22 unmixed or mixed with some oil from tank Or they may be saved for other purposes. The temperature of condenser 35 is kept at such a degree, as to condense everything condensable, the fixed gases being allowed to pass out of pipe 36 and they may be conveyed by a pump 36 to any place where they can be utilized. The condensate from condenser 35 may then be distilled fractionally and purified in any of the known ways for pure gasolene and similar products.

' One advantage of this process is also, that no coke crusts form inside of the still, for the reason that no overheating needs take place, and what little forms is washed down and forms a slush with some of the heavy oils, which can be easily washed out through pipe 42. The decomposition all in all is more under control and can be regulated so that less fixed gas and carbon result than in a still heated by direct fire.

I claim:

Process of producing gasolene from crude oil, its products or similar oil consisting in spraying into the vapor space of the retort, and so into the liquid to be distilled, a heated liquid which is practically indiatillable in the circumstances of the operation and is insoluble in the liquid to be distilled, then withdrawing it from the liquid to be distilled to pass through a heater to be returned in cyclic course to the retort, the evolved vapor being meantime continuously collected from the retort.

W. A. STILLIANO, Jr., JNo. B. Caowr OVER. 

